Method for forming a film

ABSTRACT

A method for forming a thin film on a surface of an object to be processed by using an organic metal raw material gas within a processing chamber configured to exhaust air includes: hydrophobizing a surface of the processing chamber by introducing a hydrophobic gas into the processing chamber without the object to be processed accommodated in the processing chamber; and forming the thin film by introducing the organic metal raw material gas into the processing chamber with the object to be processed accommodated in the processing chamber.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a 35 U.S.C. §371 national stage filing ofInternational Application No. PCT/JP2010/062242, filed Jul. 21, 2010,the entire contents of which are incorporated by reference herein, whichclaims priority to Japanese Patent Application No. 2009-170837, filedJul. 22, 2009, the entire contents of which are incorporated byreference herein.

TECHNICAL FIELD

The present disclosure relates to a device and method for forming a thinfilm, such as for example a manganese (Mn)-containing film, as abarrier/seed film on the surface of an object to be processed such as asemiconductor wafer, or the like.

BACKGROUND

In general, in fabricating a semiconductor device, various processessuch as film formation, pattern etching, and the like, are repeatedlyperformed on a semiconductor wafer to fabricate a desired device. Assemiconductor devices are required to be highly integrated and fine, aline width or a hole diameter is increasingly reduced. According to onerelated art, as a material of a wiring or a material to be buried in arecess such as a trench, a hole, or the like, copper, which has verysmall electric resistance and is low-priced, tends to be used since itis necessary to reduce electric resistance due to the reduction invarious dimensions. Also, when copper is used as a wiring material orburied material, a tantalum (Ta), tantalum nitride film (TaN), or thelike is generally used as a barrier layer in consideration of diffusionbarrier properties, or the like of copper thereunder.

In order to bury copper in the recess, in a plasma sputtering apparatus,a thin seed film formed of a copper film is first formed on the entiresurface of the wafer including all the faces of the wall within therecess, and the entire surface of the wafer is then plated with copper.Accordingly, the interior of the recess is totally buried. Thereafter,the remaining copper thin film on the surface of the wafer is polishedand removed through chemical mechanical polishing (CMP), or the like.

Recently, various techniques have been developed to further improve thereliability of the barrier layer. Among them, a self-formation barrierlayer using a manganese (Mn) film or a copper-manganese (CuMn) alloyfilm, instead of Ta film or TaN film, has come to prominence in anotherrelated art. The Mn film or CuMn alloy film are formed throughsputtering, and the Mn film or CuMn alloy film itself is used as a seedfilm. Thus, a Cu-plated layer may be formed directly at an upper portionof the Mn film or the CuMn alloy film, and after plating the Cu platedlayer, annealing may be performed. Then, the Cu-plated layer is reactedwith an SiO₂ layer, the underlying insulting film, in a manner ofself-alignment to form a barrier film called MnSixOy (where x and y areeach a certain positive integer) or MnOx (where x is a certain positiveinteger), a manganese oxide, at the boundary between the SiO2 layer andthe Mn film or the CuMn alloy film. Namely, the number of fabricationprocesses can be reduced.

However, the method of forming the Cu film or the CuMn alloy filmthrough sputtering does not have good coverage, which may fail tosufficiently cope with the trend of fabricating a highly finesemiconductor device. Thus, recently, research for forming these filmsaccording to CVD has been conducted. Also, multiple types of manganeseoxides such as MnO, Mn₃O₄, Mn₂O₃, MnO₂, or the like exist depending onthe degree of Mn, which will be generally referred to as MnO_(x) in thepresent specification.

Here, as mentioned above, when forming the Mn film and the CuMn alloyfilm by using a film forming device, a thermal CVD method is generallyused. In this case, however, a great amount of sediment adheres on aninner surface of a processing chamber of the film forming device, on asurface of an inner structure within the processing chamber, and on aninner wall or on a surface of an inner structure of an exhaust pipereaching a trap of an exhaust system, a pressure regulation valve (APC),a vacuum pump, or the like. As a result, the frequency of a cleaningprocess is increased or a great amount of particles is generated due todelamination of the sediment. These problems are severe because a filmformation rate increases when an oxygen-containing gas such as H₂O, orthe like is added as a reactant gas.

SUMMARY

The present disclosure provides a device and method for forming a filmcapable of restraining sediment from adhering on the surface of a memberexposed to an atmosphere within a processing chamber.

According to one embodiment of the present disclosure, in a film formingapparatus for forming a thin film on a surface of an object to beprocessed by using an organic metal raw material gas within a processingchamber configured to exhaust air (atmosphere), a hydrophobic layer isinstalled on a surface of a member exposed to the atmosphere within theprocessing chamber.

According to one embodiment of the present disclosure, in a film formingapparatus for forming a thin film on a surface of an object to beprocessed by using an organic metal raw material gas and anoxygen-containing gas within a processing chamber configured to exhaustair, a hydrophobic layer is installed on a surface of a member exposedto the atmosphere within the processing chamber.

According to one embodiment of the present disclosure, in a film formingmethod for forming a thin film on a surface of an object to be processedby using an organic metal raw material gas within a processing chamberconfigured to exhaust air, the method comprises: hydrophobizing asurface of the processing chamber by introducing a hydrophobic gas intothe processing chamber without the object to be processed accommodatedin the processing chamber; and forming the thin film by introducing theorganic metal raw material gas into the processing chamber with theobject to be processed accommodated in the processing chamber.

Further, according to one embodiment of the present disclosure, in afilm forming method for forming a thin film on a surface of an object tobe processed by using an organic metal raw material gas within aprocessing chamber configured to exhaust air, the method comprises:forming a silicon layer on a surface of a member exposed to theatmosphere within the processing chamber in advance; hydrophobizing asurface of the silicon layer by introducing a hydrophobic gas into theprocessing chamber without the object to be processed accommodated inthe processing chamber; and forming the thin film by introducing theorganic metal raw material gas into the processing chamber with theobject to be processed accommodated in the processing chamber.

BRIEF DESCRIPTION OF THE DRAWINGS

The accompanying drawings, which are incorporated in and constitute apart of the specification, illustrate embodiments of the disclosure, andtogether with the general description given above and the detaileddescription of the embodiments given below, serve to explain theprinciples of the disclosure.

FIG. 1 is a view illustrating the configuration of one example of adevice for forming a film according to the present disclosure.

FIG. 2 is a partial enlarged sectional view showing a hydrophobic layerformed on a surface of each member of the film forming device.

FIGS. 3A and 3B are views showing a process of one example ofhydrophobic processing.

FIG. 4 is a graph showing experiment results of evaluating a filmthickness of a film deposited on the hydrophobic layer used in the filmforming device of the present disclosure.

FIG. 5 is a flowchart illustrating one example of a film forming methodaccording to the present disclosure.

DETAILED DESCRIPTION

Hereinafter, one example of a film forming device and a film formingmethod according to the present disclosure will be described withreference to the accompanying drawings. FIG. 1 is a view illustratingthe configuration of one example of a device for forming a filmaccording to the present disclosure, FIG. 2 is a partial enlargedsectional view showing a hydrophobic layer formed on a surface of eachmember of the film forming device of FIG. 1, and FIG. 3 is a viewshowing a process of one example of hydrophobic processing. The filmforming device is a device for forming an Mn-containing film as a thinfilm by using an organic metal gas and an oxygen-containing gas. Also,in the following description, a case in which water vapor (H₂O) is usedas an oxygen-containing gas will be taken as an example.

As illustrated, a film forming device 2 according to the presentembodiment includes a processing chamber 4 which is made of, forexample, an aluminum material or an aluminum alloy material, and aninternal section of which has a substantially circular shape. A showerhead unit 6, as a gas introduction unit for introducing required gas,e.g., a film formation gas, or the like is installed at the ceilingportion of the processing chamber 4. Various gases required for forminga film are sprayed toward a processing space S from a plurality of gasinjection holes 10A and 10B installed on a gas injection face 8 of alower portion thereof.

Two demarcated hollow gas diffusion spaces 12A and 12B are formed withinthe shower head unit 6. A processing gas introduced into the respectivegas diffusion spaces 12A and 12B is diffused in a planar direction andthen exhausted from the respective gas injection holes 10A and 10B incommunication with the respective gas diffusion spaces 12A and 12B.Namely, the gas injection holes 10A and 10B are disposed in a matrixform, and respective gases sprayed from the respective gas injectionholes 10A and 10B are mixed in the processing space S.

This type of gas supply is called a post-mix. The entirety of the showerhead unit 6 is made of, for example, nickel, a nickel alloy such asHastelloy® or the like, aluminum, or an aluminum alloy. If a film isformed through ALD to be described later, a structural aspect in whichonly one gas diffusion space is provided in the shower head unit 6 maybe employed. A sealing member 14 configured as, for example, an O ringor the like may be interposed at a connection portion between the showerhead unit 6 and an upper opening portion of the processing chamber 4 tomaintain air-tightness of the interior of the processing chamber 4.

Also, an entrance/exit 16 for allowing a semiconductor wafer W, as anobject to be processed, to be carried in or out of the processingchamber 4 therethrough is formed at a side wall of the processingchamber 4. A gate valve 18 is installed on the entrance/exit 16 so as tobe opened and closed air-tightly.

Further, an exhaust space 22 is formed at a lower portion 20 of theprocessing chamber 4. More specifically, a large opening 24 is formed ata central portion of the lower portion 20 of the chamber, and acylindrical partition wall 26 which has a bottom of a cylindrical shapeand extends downward is connected to the corresponding opening 24 andthe interior of the cylindrical partition wall 26 forms (demarcates) theexhaust space 22. A mounting table structure 30 is installed on a bottomportion 28 of the cylindrical partition wall 26 such that it stands upon the bottom portion 28. Specifically, the mounting table structure 30is configured to mainly include a cylindrical support 32 standing up onthe bottom portion 28 and a mounting table 34 fixed to an upper endportion of the support 32 and allowing the semiconductor wafer W, anobject to be processed, to be mounted on an upper surface thereof.

The mounting table 34 is made of, for example, a ceramic material,quartz glass, or aluminum (also including an aluminum alloy). Aresistance heater 36 configured as, for example, a carbon wire heater,or the like for generating heat through electrical connection iscontained as a heating unit in the mounting table 34. Accordingly, thesemiconductor wafer W mounted on the upper surface of the mounting table34 can be heated.

A plurality of, e.g., three, pin insertion holes 38 are formed in apenetrative manner in a vertical direction in the mounting table 34(only two pin insertion holes are illustrated in FIG. 1). Push-up pins40 are disposed in the respective insertion holes 38 in a state thatthey are inserted so as to be movable up and down. Push-up rings 42 madeof, for example, a ceramic material such as alumina, and having acircular ring shape are disposed at lower ends of the push-up pins 40,respectively. Namely, the lower ends of the respective push-up pins 40are supported by the push-up rings 42. An arm portion 44 extending fromthe push-up ring 42 is connected to an appearance/disappearance rod 46installed to penetrate the bottom portion 20 of the chamber. Theappearance/disappearance rod 46 is lifted and lowered by an actuator 48.

Accordingly, when the wafer W is carried in or out, the respectivepush-up pins 40 can be protruded from upper ends of the respective pininsertion holes 38 to an upper side or retreated therefrom. Also, aretractable bellows 50 is installed in a through portion of the bottomportion of the chamber of the appearance/disappearance rod 46, and theappearance/disappearance rod 46 can ascend or descend while maintainingair-tightness in the interior of the processing chamber 4.

The opening 24 at the entrance of the exhaust space 22 is configured tobe smaller than the diameter of the mounting table 34, and a gas flowingat an outer side of a circumferential portion of the mounting table 34moves to a lower side of the mounting table 34 and then flows to theopening 24. Also, an exhaust port 52 is formed on a lower side wall ofthe cylindrical partition wall 26 such that it faces the exhaust space22. A vacuum exhaust system 54 is connected to the exhaust port 52. Thevacuum exhaust system 54 has an exhaust passage 56 formed by an exhaustpipe 110 connected to the exhaust port 52, and a pressure regulationvalve 58, a vacuum pump 60, an abatement device (not shown), and thelike are sequentially installed in the exhaust passage 56. Accordingly,air can be exhausted by controlling the pressure of the atmosphere inthe processing chamber 4 and the exhaust space 22. And, a rubber heater112, or the like is wound on the exhaust pipe 110 to perform heating ata certain temperature.

Further, heating units, e.g., cartridge heaters 62, 64, 114, and 116 areburied in a side wall of the processing chamber 4, a side wall of theshower head unit 6, a side wall of the cylindrical partition wall 26,and the bottom portion 28 of the cylindrical partition wall 26 in orderto maintain a raw material gas at a certain temperature, e.g., at 80degrees C., to prevent the raw material gas from being re-liquefied.

Also, a raw material gas supply unit 66 for supplying a raw material gasand an oxygen-containing gas supply unit 68 for supplying anoxygen-containing gas, e.g., water vapor (H₂O), are connected to theshower head unit 6 in order to supply a certain gas to the shower headunit 6.

The raw material gas supply unit 66 has a raw material gas flow path 72connected to a gas entrance 70 of the gas diffusion space 12A in onedirection among two gas diffusion spaces. A switching valve 74 isinstalled at a midway point of the raw material gas flow path 72, andthe raw material gas flow path 72 is connected to a first raw materialsource 78 for containing a first raw material by way of the switchingvalve 74. Also, a flow rate controller 76 such as a mass flow controlleris installed on the raw material gas flow path 72 at an upper streamside of the first raw material source 78 in order to regulate a flowrate of a bubbling gas.

As a first raw material, an organic metal raw material including metalis used. For example, a raw material gas may be bubbled by an inert gas,such as a flow rate-controlled Ar gas, or the like so as to be gasified,whereby the organic metal raw material may be supplied along with theinert gas. Here, when a vapor pressure of the raw material is low, thefirst raw material source 78 is heated by a heater (not shown), or thelike in order to increase the vapor pressure of the raw material. As theorganic metal raw material, for example, (EtCp)₂Mn (precursor:cyclopentadienylmanganese) including manganese is stored in a liquidstate in the first raw material source 78. Also, a rare gas such as He,Ne, or the like, or N₂ or H₂, instead of Ar gas, may be used as theinert gas for bubbling.

Further, a tape heater 80 is wound around the raw material gas flow path72 or the switching valve 74 installed at the raw material gas flow path72 in order to prevent the raw material gas from being re-liquefied, andthese are heated at, for example, 80 degrees C. Also, of course, aplurality of raw material gas supply units may be installed depending ona raw material in use.

The oxygen-containing gas supply unit 68 includes a gas flow path 84connected to a gas entrance 82 of the other gas diffusion space 12B. Aswitching valve 86 and a flow rate controller 88 such as a mass flowcontroller are sequentially installed in the midway points of the gasflow path 84, connecting the gas flow path 84 to a water vapor source 90for generating water vapor. The water vapor source 90 may be configuredas, for example, a water tank. The water tank may be maintained at, forexample, about 40 degrees C., by, for example, a temperature regulator92, and generates water vapor by increasing a vapor pressure.

Also, a tape heater 94 is wound around the flow rate controller 88without the gas flow path 84 and the switching valve 86 installed at thegas flow path 84, in order to prevent water vapor from beingre-liquefied, and these are heated at, for example, 80 degrees C.

In the present embodiment, the raw material gas is introduced into thegas diffusion space 12A positioned at an upper side of the shower headunit 6, and the oxygen-containing gas (water vapor) is introduced intothe gas diffusion space 12B positioned at a lower side of the showerhead unit 6. This is because, since the shower head unit 6 is inproximity to the mounting table 34, the temperature of the gas injectionface 8 is increased. Namely, if the raw material gas is introduced intothe lower gas diffusion space 12B, the raw material gas would likelydecompose.

Also, although not shown, a purging inert gas supply unit is connectedto the shower head unit 6, and a purging gas may be supplied asnecessary. As the purging gas, an inert gas such as N₂ gas, Ar gas, Hegas, Ne gas, or the like may be used. And, a hydrophobic layer 96, whichis the feature of the present disclosure, is installed on the surfacesof members exposed to the atmosphere within the processing chamber 4.

More specifically, in the present embodiment, the members include theprocessing chamber 4, the shower head unit 6, the mounting tablestructure 30, the gate valve 18, and the like. Namely, they include theinner surface of the processing chamber 4 (also including the innersurface of the cylindrical partition wall 26), the lower surface of theshower head unit 6, respective surfaces of the mounting table 34,respective surfaces of the support 32, the inner surface of the gatevalve 18, and the like, and the surfaces directly exposed to theatmosphere within the processing chamber 4. And the hydrophobic layer 96is installed on those surfaces. The situation in this case is shown inFIG. 2. Namely, the hydrophobic layer 96 is installed on the surfaces ofthe respective members represented by the processing chamber 4, and thelike. The surface of the hydrophobic layer 96 is hydrophobic. Thus,adhesion of sediment on the respective surfaces of the hydrophobic layer96 is suppressed. Also, in this case, in order to sufficiently exert thesediment adhesion suppression effects, the hydrophobic layer 96 may beformed on at least the inner surface of the processing chamber 4. Inaddition, the hydrophobic layer 96 is preferably installed on an innersurface of the exhaust pipe 110 connected to the processing chamber 4,or the inner wall or an inner structure of the pressure regulation valve58 and the vacuum pump 60.

As the hydrophobic layer 96, specifically, an SiOC layer, a fluorinatedresin layer, a lubricated alumite or hydrophobic heat-resistant paint,or a hydrophobized silicon layer may be used. Such hydrophobic layer 96is formed to have a thickness ranging, for example, from 0.01 to 5 mm.In the SiOC layer, the SiOC material itself is hydrophobic. As the SiOClayer, an SiOC material having a dense interior, or an SiOC materialbeing porous therein may be used. In one example, as the SiOC layer,Black Diamond®, Aurora ULK®, or the like may be used. Also, in thefluorinated resin layer, the fluorinated resin material itself ishydrophobic. As the fluorinated resin layer, for example, Teflon® may beused. Also, the lubricated alumite is formed by charging (filling) fattyacid such as oleic acid or the like, graphite, or a Teflon resin(fluorinated resin) in fine pores of a hard alumite coated film, and italso includes an alumite obtained by adsorbing fine particles of polytetrafluoreethylene (PTFE).

Also, the silicon layer is formed on the surfaces of the respectivemembers of the processing chamber 4, or the like by a silicon thermalspray process, for example. In this case, as shown in FIGS. 3A and 3B,the surface of the silicon layer 100 is terminated with an —OH groupwhich is a hydrophilic group, so hydrophobization (or hydrophobictreatment) is performed on the surface of the silicon layer 100 to makethe surface hydrophobic, thus forming the hydrophobic layer 96. Examplesof the hydrophobization may include a method for HF-cleansing thesurface of the silicon layer 100 as shown in FIG. 3A and a method ofprocessing the surface of the silicon layer 100 withhexamethyldisilazane (HMDS)[=(CH₃)₃Si—NH—Si(CH₃)₃] as shown in FIG. 3B.By performing HF cleansing, the —OH group on the surface of the siliconlayer 100 is substituted with a —H and hydrogen-terminated as shown inFIG. 3A. Accordingly, hydrophobicity can be exhibited. Or, by performingHMDS, the —OH group on the surface of the silicon layer 100 is reactedwith HMDS so as to be silylated and Si and three methyl groups arebonded as shown in FIG. 3B. Accordingly, hydrophobicity can beexhibited. Also, as shown in FIG. 3B, R1, R2, and R3 are not limited tothe methyl groups, but they may be alkyl groups.

Preferably, before the film forming device 2 is assembled, i.e., in astate the respective members exist as unassembled parts, theabove-mentioned hydrophobic layer 96 is selectively formed on thesurfaces which are to be exposed to the atmosphere within the processingchamber 4 after assembling the film forming device 2.

Referring back to FIG. 1, in order to control the overall operation ofthis device, for example, a control unit 102 configured as a computer,or the like is installed. The control unit 102 controls the initiationand the termination of the supply of respective gases, a supply amountof the respective gases, the pressure within the processing chamber 4,the temperature of the wafer W, and the like. Also, the control unit 102includes a storage medium 104 for storing a computer program forperforming the foregoing control, or a user interface 106. As thestorage medium 104, for example, a flexible disk, a flash memory, a harddisk, a compact disc (CD), or the like may be used. The user interface106 is configured as a keyboard for allowing an operator to input andoutput a command to manage the film forming device 2, a display forvisually displaying an actuation state of the film forming device 2, andthe like.

Next, the operation of the film forming device 2 configured as describedabove will be described. First, the surface of the unprocessedsemiconductor wafer W is covered by, for example, an insulating layersuch as an interlaying insulating layer or the like, and thesemiconductor wafer W has trenches such as a contact hole, a via hole,or a wiring recess, reaching an underlying wiring layer, previouslyformed therein. Such a wafer W is maintained by a carrying arm (notshown) and carried into the processing chamber 4 through the gate valve18 in an open state, and the entrance/exit 16. Also, the wafer W ishanded over to the lifted push-up pins 40. As the push-up pins 40 arelowered, the wafer W is mounted on an upper surface of the mountingtable 34.

Then, the raw material gas supply unit 66 or the oxygen-containing gassupply unit 58 operates, and respective gases, whose flow rates arecontrolled, are supplied to the shower head unit 6 and sprayed from thegas injection holes 10A and 10B so as to be introduced into theprocessing space S. Various gas supply aspects exist, as will bedescribed later. Here, an Mn-containing raw material gas and water vaporare supplied.

Also, the vacuum pump 60 installed in the vacuum exhaust system 54 iscontinuously driven to exhaust air within the processing chamber 4 orthe exhaust space 22. And, the degree of opening the pressure regulationvalve 58 is adjusted to maintain the atmosphere of the processing spaceS at a certain processing pressure. At this time, the wafer W is heatedby the resistance heater 36 installed in the mounting table 34 andmaintained at a certain processing temperature. In this case, theprocessing temperature of the wafer W is about 200 degrees C. Also, theshower head unit 6 or the processing chamber 4 is heated to have atemperature, e.g., about 80 degrees C., at which the Mn raw material gasis prevented from being re-liquefied.

Accordingly, a desired thin film is formed on the surface of thesemiconductor wafer W. In this case, the Mn-containing film is formed asa thin film on the surface of the wafer W. The Mn-containing film maybe, specifically, MnO_(x) film (manganese oxide film), and may beMnSi_(x)O_(y) which has been reacted with an underlying base, dependingon circumstances.

A gas supply aspect in this case, as in yet another related art, forexample, includes a method of forming a thin film through thermal CVD bysimultaneously supplying an Mn-containing raw material gas and watervapor, and an atomic layered deposition (ALD) method of repeatedlyperforming a raw material gas adsorption process and a reaction processby alternately intermittently supplying the Mn-containing raw materialgas and water vapor repeatedly. Any supply aspect (film forming method)may be used. In the ALD method, the adsorption of the raw material gasand the reaction by supplying water vapor are alternately performed tostack a thin film having a thickness of an atomic level or a molecularlevel one by one repeatedly.

In the film forming process as described above, in case of theconventional film forming device, when the Mn-containing raw materialgas or water vapor is supplied into the processing chamber, the rawmaterial gas or water vapor tend to be attached to the surfaces of themembers exposed to the atmosphere within the processing chamber, e.g.,the inner surface of the processing chamber, the gas injection face ofthe shower head unit, the surface of the mounting table, the innersurface of the gate valve, and the like, and the Mn-containing thin filmis unnecessarily deposited thereon.

However, in the film forming device 2 according to the presentembodiment, as described above, since the hydrophobic layer 96 isinstalled on each of the surfaces of the members exposed to theatmosphere within the processing chamber 4, i.e., the inner surface ofthe processing chamber 4, the gas injection face 8 of the shower headunit 6, the surface of the mounting table structure 30 including themounting table 34 and the support 32, and the inner surface of the gatevalve 18, the Mn-containing raw material gas or water vapor iseffectively restrained from being attached to the surfaces of therespective members.

In particular, when a raw material such as (EtCp)₂Mn is used as anMn-containing raw material, since cyclo pentadienyl (Cp) is aromaticusand has π electrons, it is considered difficult for the Mn-containingraw material itself to be adsorbed to the surface of the hydrophobicmember. As an Mn raw material having this cyclo pentadienyl ligand, forexample, (EtCp)₂Mn[═Mn(C₂H₅C₅H₄)₂], Cp₂Mn[═Mn(C₅H₅)₂],(MeCp)₂Mn[═Mn(CH₃C₅H₄)₂], (i-PrCp)₂Mn[═Mn(C₃H₇C₅H₄)₂],MeCpMn(CO)₃[═(CH₃C₅H₄)Mn(CO)₃], (t-BuCp)₂Mn[═Mn(C₄H₉C₅H₄)₂],Mn(DMPD)(EtCp)[═Mn(C₇H₁₁C₂H₅C₅H₄)], ((CH3)₅Cp)₂Mn[═Mn((CH₃)₅C₅H₄)₂ maybe used. Namely, one or more materials selected from the groupconsisting of these materials may be used. In this case, attachment anddeposition of unnecessary sediment on the surfaces of the respectivemembers can be more effectively prevented. Thus, the generation ofparticles due to delamination of the unnecessary sediment can beconsiderably restrained. Also, down time of the device according tomaintenance such as cleaning, or the like within the processing chambercan be reduced, and operational cost can also be reduced.

Next, an experiment of evaluating the hydrophobic layer 96 used for thefilm forming device as described above was performed. The results willbe described. Here, a chip (small piece) having a surface with materialsconstituting respective hydrophobic layers formed thereon was installedon the mounting table within the processing chamber, 200 degrees C., asthe same processing temperature as that in forming the MnO_(x) film, wasmaintained, and the same film forming processing as that of MnO_(x) filmas described was performed for 10 minutes.

Also, for a comparison, the same film forming processing was performedon a chip of an aluminum alloy used as a constituent material of theprocessing chamber which was not subjected to hydrophobization and achip having an SiO₂ film formed on a surface thereof by using TEOS as arepresentative of a hydrophilic surface. The results in this case areshown in FIG. 4. FIG. 4 is a graph showing a film thickness of the filmsdeposited on the respective surface layers.

As shown in FIG. 4, the MnO_(x) film having a thickness of about 4.2 nmis formed to be thick on the surface of the SiO₂ film chip which is ahydrophilic surface formed by using TEOS. This is undesirable.

In comparison, in case of using the hydrophobic layer disclosed in thepresent disclosure, it can be seen that the thickness of the depositedMnO_(x) film is restrained in every material, so it is very thin.Namely, it can be seen that the film thickness of the chip having theHF-treated (hydrophobized) silicon layer was about 0.5 nm, that of thechip having the SiOC layer (Black Diamond) was about 0.2 nm, and that ofthe chip having the porous SiOC layer was about 0.6 nm, the results ofall of which are good.

In the film forming device 2 according to the present embodiment, beforethe film forming device 2 is assembled, the hydrophobic layer 96 isformed on the required surfaces of the respective members, but thepresent disclosure is not limited thereto. For example, when a siliconlayer is used as the hydrophobic layer 96, hydrophobization may beperformed before forming the Mn-containing film after the film formingdevice is assembled.

FIG. 5 is a flowchart illustrating a process of an example in such acase. More specifically, a hydrophobizing process is performed (S1).Namely, within the processing chamber 4 of the film forming device 2fabricated by assembling respective members with a silicon layer formedthereon, with the wafer W not accommodated yet, a hydrophobic gas isallowed to flow into the processing chamber 4 from a gas source (notshown), and the surface of the silicon layer formed on the surface ofeach of the members is hydrophobized. The hydrophobic gas, HF gas orHMDS gas may be used. Accordingly, the surface of the silicon layerformed on the surfaces of the respective members, that is, the innersurface of the processing chamber 4, the gas injection face 8 of theshower head unit 6, the surface of the mounting table structure 30, orthe surface of the gate valve 18 is hydrophobized to form thehydrophobic layer 96 as shown in FIG. 3.

Accordingly, as shown in FIG. 1, the hydrophobic layer 96 is formed oneach of the surfaces of the respective members. Thereafter, as describedabove, a thin film forming process is performed (S2). Namely, theMn-containing raw material gas and water vapor are allowed to flow intothe processing chamber 4 to form the MnO_(x) film. Also in this case,since the hydrophobic layer 96 is formed on the surface of each of themembers, the same working effects as that described above can beachieved. Further, the foregoing hydrophobization is performed on thesilicon layer attached to the surface of each of the members, but thepresent disclosure is not limited thereto, and hydrophobization may beperformed directly on the respective members without installing thesilicon layer on the surface thereof.

In addition, in the foregoing embodiment, the same material is used forthe hydrophobic layer 96 of each member, but the present disclosure isnot limited thereto and various materials may be separately combined.For example, an SiOC layer may be installed as the hydrophobic layer 96on the inner surface of the processing chamber 4, and an HF-treatedsilicon layer may be installed as the hydrophobic layer 96 on the gasinjection face 8 of the shower head unit 6.

Also, in the foregoing embodiment, water vapor was used as anoxygen-containing gas as an example, but the present disclosure is notlimited thereto, and as the oxygen-containing gas, one or more selectedfrom the group consisting of H₂O (water vapor), N₂O, NO₂, NO, O₃, O₂,H₂O₂, CO, CO₂, alcohols, and organic acid may be used. The alcohols mayinclude a methyl alcohol, an ethyl alcohol, and the like.

Additionally, in the foregoing embodiment, the Mn-containing rawmaterial gas and the oxygen-containing gas were used and the MnO_(x)film was used as a thin film as an example, but the present disclosureis not limited thereto. Namely, the present disclosure may also beapplicable to a case where the Mn film is formed as a thin film by usingthe Mn-containing raw material gas, without using the oxygen-containinggas.

Also, in the foregoing embodiment, (EtCp)₂Mn was used as theMn-containing raw material as an example, but the present disclosure isnot limited thereto, and as the Mn-containing raw material, one or moreselected from the group consisting of (EtCp)₂Mn[═Mn(C₂H₅C₅H₄)₂],Cp₂Mn[═Mn(C₅H₅)₂], (MeCp)₂Mn[═Mn(CH₃C₅H₄)₂],(i-PrCp)₂Mn[═Mn(C₃H₇C₅H₄)₂], MeCpMn(CO)₃[═(CH₃C₅H₄)Mn(CO)₃],(t-BuCp)₂Mn[═Mn(C₄H₉C₅H₄)₂], CH₃Mn(CO)₅, Mn(DPM)₃[═Mn(C₁₁H₁₉O₂)₃],Mn(DMPD)(EtCp)[═Mn(C₇H₁₁C₂H₅C₅H₄)], Mn(acac)₂[═Mn(C₅H₇O₂)₂],Mn(DPM)₂[═Mn(C₁₁H₁₉O₂)₂], Mn(acac)₃[═Mn(C₅H₇O₂)₃],Mn(hfac)₂[═Mn(C₅HF₆O₂)₃], ((CH₃)₅Cp)₂Mn[═Mn((CH₃)₅C₅H₄)₂],[Mn(iPr-AMD)₂][═Mn(C₃H₇NC(CH₃)NC₃H₇)₂], and[Mn(tBu-AMD)₂][═Mn(C₄H₉NC(CH₃)NC₄H₉)₂] may be used.

Further, in the foregoing embodiment, Mn was taken as an example ofmetal included in the organic metal raw material gas, but the presentdisclosure is not limited thereto. As the metal included in the organicmetal raw material gas, one or more selected from the group consistingof Mn, Nb, Zr, Cr, V, Y, Pd, Ni, Pt, Rh, Tc, Al, Mg, Sn, Ge, Ti, and Remay be used.

Also, in the foregoing embodiment, HF gas or HMDS gas was taken as anexample of the hydrophobic gas, but the present disclosure is notlimited thereto. As the hydrophobic gas, one or more gases selected fromthe group consisting of HF, HMDS(Hexamethyldisilazane),TMDS(1,1,3,3-Tetramethyldisilazane),TMSDMA(Dimethylaminotrimethylsilane),DMSDMA(Dimethylsilyldimethylamine), TMMAS(Trimethylmethylaminosilane),TMICS(Trimethyl(isocyanato)silane), TMSA(Trimethylsilylacetylene), andTMSC(Trimethylsilylcyanide5), 1,3,5,7-tetramethylcyclotetrasiloxane,dimethylsilane, tetraethylcyclotetrasilosane,1,2,3-triethyl-2,4,6-trimethylcyclotrisilazane,1,2,3,4,5,6-hexamethylcyclotrisilazane, monomethylsilane,hexamethyldisilane, hexamethylsiloxane, trimethylsilane,tetramethylsilane, dimethyldimethoxysilane,octamethylcyclotetrasiloxane, trimethoxymethylsilane,hexaethyldisilazane, hexaphenyldisilazane, heptamethyldisilazane,dipropyl-tetramethyldisalazane, di-n-butyl-tetramethyldisilazane,di-n-octyl-tetramethyldisilazane, divinyl-tetramethyldisilazane,1,1,3,3,5,5-hexamethylcyclotrisilazane, hexaethylcyclotrisilazane,hexaphenylcyclotrisilazane, octamethylcyclotrisilazane,octaethylcyclotrisilazane, tetraethyl-tetramethylcyclotrisilazane,tetraphenyldimethyldisilazane, diphenyl-tetramethyldisilazane,trivinyl-trimethylcyclotrisilazane, andtetravinyl-tetramethylcyclotetrasilazane may be used.

According to the present disclosure in some embodiments, since thehydrophobic layer is installed on the surface of the member exposed tothe atmosphere within the processing chamber, the attachment of sedimenton the surfaces of the member can be effectively restrained.

Furthermore, the semiconductor wafer is described here as an example ofthe object to be processed, but the semiconductor wafer includes asilicon substrate or a compound semiconductor substrate such as GaAs,SiC, GaN, or the like. Also, without being limited thereto, the presentdisclosure may also be applicable to a glass substrate, a ceramicsubstrate, or the like used for a liquid crystal display device.

What is claimed is:
 1. A film forming method for forming a thin film ona surface of an object to be processed by using an organic metal rawmaterial gas within a processing chamber configured to exhaust air, themethod comprising: hydrophobizing a surface of the processing chamber byintroducing a hydrophobic gas into the processing chamber without theobject to be processed accommodated in the processing chamber; andforming the thin film by introducing the organic metal raw material gasinto the processing chamber with the object to be processed accommodatedin the processing chamber.
 2. A film forming method for forming a thinfilm on a surface of an object to be processed by using an organic metalraw material gas within a processing chamber configured to exhaust air,the method comprising: forming a silicon layer on a surface of a memberexposed to the atmosphere within the processing chamber in advance;hydrophobizing a surface of the silicon layer by introducing ahydrophobic gas into the processing chamber without the object to beprocessed accommodated in the processing chamber; and forming the thinfilm by introducing the organic metal raw material gas into theprocessing chamber with the object to be processed accommodated in theprocessing chamber.
 3. The method of claim 1, wherein the hydrophobicgas is configured as one or more gases selected from the groupconsisting of HF, HMDS(Hexamethyldisilazane),TMDS(1,1,3,3-Tetramethyldisilazane),TMSDMA(Dimethylaminotrimethylsilane),DMSDMA(Dimethylsilyldimethylamine), TMMAS(Trimethylmethylaminosilane),TMICS(Trimethyl(isocyanato)silane), TMSA(Trimethylsilylacetylene), andTMSC(Trimethylsilylcyanide5), 1,3,5,7-tetramethylcyclotetrasiloxane,dimethylsilane, tetraethylcyclotetrasilosane,1,2,3-triethyl-2,4,6-trimethylcyclotrisilazane,1,2,3,4,5,6-hexamethylcyclotrisilazane, monomethylsilane,hexamethyldisilane, hexamethylsiloxane, trimethylsilane,tetramethylsilane, dimethyldimethoxysilane,octamethylcyclotetrasiloxane, trimethoxymethylsilane,hexaethyldisilazane, hexaphenyldisilazane, heptamethyldisilazane,dipropyl-tetramethyldisalazane, di-n-butyl-tetramethyldisilazane,di-n-octyl-tetramethyldisilazane, divinyl-tetramethyldisilazane,1,1,3,3,5,5-hexamethylcyclotrisilazane, hexaethylcyclotrisilazane,hexaphenylcyclotrisilazane, octamethylcyclotrisilazane,octaethylcyclotrisilazane, tetraethyl-tetramethylcyclotrisilazane,tetraphenyldimethyldisilazane, diphenyl-tetramethyldisilazane,trivinyl-trimethylcyclotrisilazane, andtetravinyl-tetramethylcyclotetrasilazane.